Sulfonium ylids



United States 3,359,322 SULFONDUM YLIDS Kenneth Wayne Ratts, Creve Coeur, Mm,

Monsanto Company, St. Louis, Mo, Delaware No Drawing. Filed May 11, 1966, Ser. No. 549,166 11 Claims. (Cl. 260-592) assignor to a corporation of ABSTRACT OF THE DISCLOSURE Compounds of the formula RCHz (I) S=CHCZ wherein R and R are each selected from the group consisting of hydrogen, alkyl of not more than 12 carbon atoms and haloalkyl of not more than 12 carbon atoms containing 1, 2 or 3 halogen atoms, and Z is selected from the group consisting of naphthyl and This invention relates to sulfonium ylids. The sulfonium ylids of this invention are represented by the formula wherein R and R are each selected from the group consisting of hydrogen, alkyl of not more than 12 carbon atoms and haloalkyl of not more than 12 carbon atoms containing 1, 2 or 3 halogen atoms, and Z is selected from the group consisting of naphthyl and R h R wherein R is selected from the group consisting of halogen (Cl, Br, F and I) and alkyl of not more than 4 carbon atoms, R is selected from the group consisting of N and alkoxy of no more than 4 carbon atoms, R is phenyl, a is an integer from 0 to 5 inclusive, b is an integer from O to 2 inclusive and c is an integer from 0 to 1.

In the above formula R and R can be hydrogen, alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, secbutyl, isobutyl, tert-butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl and the various homologues and isomers of alkyl having from 1 to 12 carbon atoms and haloalkyl such as chloromethyl, iodomethyl, bromomethyl, fluoromethyl, chloroethyl, iodoethyl, bromoethyl, fiuoroethyl, trichloromethyl, triiodomethyl, tribromomethyl, trifluoromethyl, dichloroethyl, chloro-n-propl, bromo-n-propyl, iodoisopropyl, bromo-n-butyl, bromo-tert-butyl, 1,3,3-trichlorobutyl, 1,3,3-tribromobutyl, chloropentyl, bromopentyl, 2,3-dichloropentyl, 3,3-dibromopentyl, chlorohexyl, bromohexyl, 2,4-dichlorohexyl, 1,3-dibromohexyl,

atent 1,3,4-trichlorohexyl, chloroheptyl, bromoheptyl, fluoroheptyl, 1,3-dichloroheptyl, 1,4,4-trichloroheptyl, 2,4-di (chloromethyl)-heptyl, chlorooctyl, bromooctyl, iodooctyl, 2,4-di(chloromethyl)hexyl, 2,4-dichlorooctyl, 2,4,4- tri (chloroinethyl) pentyl, 1,3,5 -tribromooctyl and the halogenated straight and branched chain nonyl, decyl, undecyl and dodecyl.

Representative R alkyl for the above formula include the alkyl listed above for R and R for not more than 4 carbon atoms. Representative R alkoxy for the above formula include for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy and isobutoxy.

The sulfonium ylids of the present invention are prepared by a process which comprises reacting a sulfonium salt of the formula RCHz O wherein R, R and Z are as defined above and X is halogen (Cl, Br, F and I), with a substantially equimolar amount of an alkaline material in the presence of an inert liquid media.

Temperature of reaction is critical but only in regard to the upper limit. The process must be carried out at a temperature below the decomposition or rearrangement temperature of the sulfonium ylid product. For example, if the process of this invention is carried out for substantial periods with sulfonium salt reactants wherein one or more of R and R in the above formula is hydrogen in the presence of aqueous or alcoholic media at temperatures above about 50 C., thermal rearrangement of the product sulfonium ylids proceeds according to the following representative synthesis wherein R and Z are as defined above. The process of this invention is generally carried out at a temperature below about 50 C. and preferably at a temperature of about 15 C. to above 30 C.

Pressure is not a critical factor in the process of this invention. Pressure both above and below atmospheric pressure can be employed although atmospheric pressure is preferred for convenience.

Alkaline materials suitable for use in the process of this invention include inorganic bases, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal hydrides such as sodium hydride, potassium hydride and lithium hydride; metallic oxides such as calcium oxide, magnesium oxide, silver oxide and barium oxide; alkali metal and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate and barium carbonate, and ammonia and ammonia producing compounds such as ammonium hydroxide and ammonium carbonate; and organic bases, for example, aliphatic and aromatic alkoxides such as sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium butoxide, sodium butoxide, sodium phenoxide, lithium phenoxide and potassium phenoxide; primary, secondary and tertiary amines such as methylamine, ethylamine, propylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, N-

methyl-N-ethylamine, N-methyl-N-isopropylamine, trimethylamine, triethylamine, tri n propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, trisec-butylamine, tri-n-arnylamine, triisoarnylamine, trihexylamine, triheptylamine and trioctylamine; other amines such as pyridine and morpholine, and mercaptides such as sodium methylmercaptide, sodium ethylmercaptide, potassium methylmercaptide and potassium phenylmercaptide.

Inert liquid media which can be used in the process of this invention include aqueous media which can optionally contain a water-miscible alcohol such as methyl alcohol, ethyl alcohol and the like; and organic media for example, alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and the like, tetrahydrofuran and ethers such as diglyme, diethyl ether, and the like. An excess of amine reactant also serves an inert liquid media.

The inorganic alkaline materials with the exception of the hydride are usually employed in the presence of aqueous media. The hydrides and the organic alkaline materials are used in the presence of inert organic media.

The separation of the product from the reaction mixture is readily accomplished. For example the salt, such as an alkali metal halogen salt formed during the reaction can be removed by filtration and the solvent can be removed by stripping or distillation, preferably low temperature vacuum distillation. The product can be purified if necessary by any of the conventional means well known in the art, e.g. selective extraction, recrystallization, elution or any suitable combination of these methods.

The sulfonium ylids of this invention are crystalline solid materials which are insoluble in water but somewhat soluble in many organic solvents, for example alcohols, ketones, hydrocarbons such as benzene, toluene, xylene and the like and chlorohydrocarbons such as chlorobenzene, carbon tetrachloride and the like.

The following examples illustrate the invention. In the following examples as well as in the specification and appended claims, parts and percent are by weight unless otherwise indicated.

Example I A suitable reaction vessel is charged with about 13.06 parts of dimethyl (phenacyl) sulfonium bromide and 250 parts of tetrahydrofuran and then 2.3 parts of sodium hydride are added with stirring at room temperature (about 25 C.). After a substantially equimolar amount of hydrogen evolves, the sodium bromide is removed by filtration and the reaction mixture is concentrated by evaporation to give a yellow oil which solidifies upon addition of petroleum ether. The solid is removed by filtration to give 8.95 parts of dimethylsulfonium phenacylide having a M.P. of 5457 C. The ylid is confirmed by nuclear magnetic resonance (NMR) and infrared spectra analysis.

Example 2 A suitable reaction vessel is charged with about 30 parts dimethyl (phenacyl) sulfonium bromide and 700 parts of water and then 45 parts of sodium hydroxide are added with stirring at room temperature (about 25 C.). The sodium bromide is removed by filtration and the water by evaporation to give 22 parts of dimethylsulfonium phenacylide. NMR and infrared spectra analysis confirm the product ylid.

Example 3 A suitable reaction vessel is charged with about 11.58 parts of silver oxide and 150 parts of Water and then a solution of dimethyl (phenacyl) sulfonium bromide in 400 parts water is added slowly with stirring at about 25 C. The precipitate which forms is removed by filtration and the filtrate is concentrated by evaporation. The concentrate is washed with trichloromethane and then the A}, trichloromethane is removed by evaporation to give 7.5 parts of dimethylsulfonium phenacylide. NMR and infrared analysis confirm the product ylid. The product ylid is recrystallized several times from petroleum ether and then dried over phosphorous pentoxide. Elemental analysis of the purified ylid gives the following:

Calcd for C H OS: C, 66.62; H, 6.71; S, 17.79. Found: C, 66.35; H, 6.91; S, 17.53.

Example 4 A suitable reaction vessel is charged with about 10 parts methyl alcohol and 0.46 part of sodium and then 2.7 parts of dimethyl (phenacyl) sulfonium bromide are added with stirring at about 25 C. The reaction mixture is concentrated by evaporation and then extracted with dichloromethane to give 1.6 parts of dimethylsulfonium phenacylide. Infrared spectrum analysis confirms the product ylid.

Example 5 A suitable reaction vessel is charged with about 15.5 parts of dimethyl (l-naphthyl) sulfonium bromide and about 250 parts of tetrahydrofuran and then 2.3 parts of sodium hydride are added with stirring at room temperature (about 25 0.). After an equirnolar amount of hydrogen evolves, the sodium bromide is removed by filtration and the tetrahydrofuran by evaporation under reduced pressure to give an orange oil which solidifies. The solid is Washed with ethyl ether to give 6.2 parts of dimethylsulfonium l-naphthacylide having a M.P. of 7275 C. The product ylid is confirmed by NMR and infrared spectra analysis.

Following substantially the same procedure as in the foregoing example the following compounds of this invention are prepared:

Example 6 dimethylsulfonium 2'-chlorophenacylide 7 dimethylsulfonium 2,5'-dichlorophenacylide 8 dimethylsulfonium 4'-chlorophenacylide 9 dimethylsulfonium 2',4-dichlorophenacylide 10 dimethylsulfonium 2',4,6'-trichlorophenacy1ide 11 dimethylsulfonium 4'-methylphenacylide 12 dimethylsulfonium 4'-tert-butylphenacylide 13 dimethylsulfonium 2',4-dimethy1phenacylide 14 dimethylsulfonium 2,4',6-trimethylphenacylide 15 dimethylsulfonium 2,5 -diethylphenacylide 16 dimethylsulfonium 2',6-di(tert-butyl)phenacylide 17 dimethylsulfonium 4-bromophenacylide 18 dimethylsulfonium 3',5-dibromophenacy1ide 19 dimethylsulfonium 2iodophenacylide 2O dimethylsulfonium 2',6-difluorophenacylide 21 dimethylsulfonium 2,5'-dimethylphenacylide 22 dimethylsulfonium 3',5'-dimethylphenacylide 23 dimethylsulfonium 2,3,4,5',6 pentachlorophenacylide 24 dimethylsulfonium 4'-nitrophenacylide 25 dimethylsulfonium 2,4'-dinitrophenacylide 26 dimethylsulfonium 4'-methoxyphenacylide 27 dimethylsulfonium 2,4-dimethoxyphenacylide 28 dimethylsulfonium 2',5-dimethoxyphenacylide 29 dimethylsulfonium 4-n-butoxyphenacylide 30 dimethylsulfonium 4'-phenylphenacylide 31 dimethylsulfonium 2'-:methyl-4-nitrophenacylide 32 dimethylsulfonium 2'-methoxy-4'-chlorophenacylide 33 dimethylsulfonium 2-methyl-4-methoxyphenacylide 34 diethylsulfonium phenacylide 35 di(n-buty1)sulfonium phenacylide 36 di(n-octyl)sulfonium phenacylide 37 di(2-chloroethyl)sulfonium phenacylide 38 di(3-chlorobutyl)sulfonium phenacylide 39 di(n-dodecyl)sulfonium phenacylide 40 di(4,4 diehloropentyl)sulfonium 4 5 chlorophenacylide 41 di(2,2,4-tribromobutyl)sulfonium phenacylide 42 di(Z-fluoropentyl)sulfonium phenacylide 43 di(2-iodoethyl)sulfonium phenacylide 44 diethylsulfonium 2',4'-dirnethylphenacylide 45 di(n-propyl)sulfonium phenacylide The sulfonium ylids of this invention are useful per se for various purposes such as fire retardants, rust inhibitors, rust removers and tanning agents, and as chemical intermediates for petroleum additives and agricultural chemicals. For example, a-hEIlOSlllfOIllllIn salts having fungicidal activity are prepared by halogenation of sulfonium ylids in accordance with the following representative synthesis:

wherein R, R R R R X, a, b, and c are as defined above. Halogenation is carried out with substantially equimolar amounts of reactants at about room temperature in the presence of inert organic media such as an aromatic hydrocarbon.

a-Halosulfoniurn ylids having fungicidal activity are prepared by a process which comprises reacting an ahalosulfonium salt of the formula wherein R, R R R R X, a, b and c are as defined above with a substantially equi-molar amount of an alkali metal hydride such as sodium hydride under substantially anhydrous conditions in the presence of an inert organic media such as tetrahydrofuran until a substantially equimolar amount of hydrogen has evolved. The above e-halosulfonium ylids and a-halosulfoniurn salts as well as more detailed processes for their preparation are disclosed and claimed in application, Serial No. 549,162 filed of even date herewith.

The sulfonium ylids of this invention are also useful in the preparation of vinyl aromatic compounds having fungicidal and nematocidal activity. The fungicidal and nematocidal vinyl aromatic compounds and processes for making them are disclosed and claimed in application, Ser. No. 549,168 filed of even data herewith.

The sulfonium salts used as starting materials in the preparation of the sulfonium ylids of this invention can be prepared by the process disclosed and claimed in application, Ser. No. 467,750, filed June 28, 1965. Said process comprises reacting a sulfide of the formula RCH SCH R wherein R and R are as defined above with a substantially equimolar amount of a compound of the formula XCHN EZ wherein Z is is defined above and X is halogen in the presence of an inert liquid medium at a temperature below the decomposition temperature of the sulfide employed.

The invention is set forth above with respect to specific examples. It is not intended that the details thereof shall be limitations on the scope of the invention except as set forth in the following claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A compound of the formula wherein R and R are each selected from the group consisting of hydrogen, alkyl of not more than 12 carbon atoms and haloalkyl of not more than 12 carbon atoms containing from 1 to 3 halogen atoms, and Z is selected from the group consisting of naphthyl and 5 wherein R is selected from the group consisting of halogen and alkyl of not more than 4 carbon atoms, R is selected from the group consisting of N0 and alkoxy of not more than 4 carbon atoms, R is phenyl, a is an integer from 0 to 5 inclusive, b is an integer from 0 to 2 inclusive, and c is an integer from 0 to 1 inclusive.

2. A compound of claim 1 wherein R and R are hydrogen.

Compound of claim 1 wherein Z is phenyl. Dimethylsulfonium phenacylide. Dimethylsulfonium 2'-chlorophenacylide. Dimethylsulfonium 4'-tert-butylphenacylide. Dimethylsulfonium 3',5'-dibromophenacylide. Dimethylsulfoniurn 4-nitrophenacylide. 9. Di(n-dodecyl)su1fonium phenacylide. 10. Dimethylsulfonium 4-phenylacylide. 11. Dimethylsulfonium l-naphthacylide.

References Cited Speziale et al., J. Am. Chem. Soc., 87, 3460-3462 (1965).

DANIEL D. HORWITZ, Primary Examiner. 

1. A COMPOUND OF THE FORMULA 